Preparation of supported silyl-capped silica-bound anion activators and associated catalysts

Abstract

A method for the preparation of olefin polymerization catalysts that are the reaction products of the catalytic reaction of surface hydroxyls of a support with a trialkyl silane to afford hydrogen and the corresponding surface bound alkyl silyl ether and at the same time with a strong Lewis acid which support is converted to a silica bound anion that in a second step is fully converted by reaction with QM 2 to the desired catalyst. Catalyst compositions are disclosed herein. Processes disclosed herein include processes for the polymerization of olefinically unsaturated monomers comprising contacting a plurality of one or more of the monomers with the catalyst.

1. A polymerization process comprising contacting one or more monomers polymerizable by coordination polymerization under suitable polymerization conditions with a polymerization catalyst formed by a method comprising:
 reacting a metal oxide support, selected from the group consisting of: silica, fumed silica, alumina, silica-alumina, magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, silica-chromium, silica-titania, aerogels, spherulites, and mixtures thereof, with at least one silane compound having the general formula: H x Si(R) 4-x , wherein x is at least 1; and R is a hydrido, alkyl, aryl, heteroalkyl, or heteroaryl ligand, in the presence of a first Lewis acid, thereby generating a silyl capped support; 
 reacting said silyl capped support with a second Lewis acid, which may be the same or different as said first Lewis acid, and an amine, thereby forming a supported silyl-capped silica-bound anion activator; and 
 reacting said supported silyl-capped silica-bound anion activator with at least one catalyst precursor, thereby forming said polymerization catalyst. 
 
     
     
       2. The process according to  claim 1 , wherein the reaction of said metal oxide support with said silane is catalyzed at a temperature in the range between 0 to 120° C. for a time period in the range between 0.1 to 10 hours. 
     
     
       3. The process according to  claim 1 , wherein the reaction of said metal oxide support with said silane is conducted in the presence of a solvent. 
     
     
       4. The process according to  claim 1 , wherein x is 2, 3 or 4. 
     
     
       5. The process according to  claim 1 , wherein said silane compound is trialkylsilane. 
     
     
       6. The process according to  claim 1 , wherein said silyl capped support comprises a trialkylsilyl content of between 1 to 99% of the available surface hydroxyl groups. 
     
     
       7. The process according to  claim 1 , wherein the reaction of said silyl capped support with a Lewis acid and said amine is conducted at temperature in the range between −80 to 150° C. for a time period in the range between 5 minutes to 24 hours. 
     
     
       8. The process according to  claim 1 , wherein the reaction of said silyl capped support with a Lewis acid and said amine is conducted in the presence of a solvent. 
     
     
       9. The process according to  claim 1 , wherein said first and/or second Lewis acid is an acid having the general formula:
   R x B(ArHal) 3-x , 
 
       where x can equal 0, 1, 2, or 3; R is a monoanionic ligand; B is boron; and ArHal is a halogenated C 6  aromatic or higher carbon number polycyclic aromatic hydrocarbon or aromatic ring assembly in which two or more rings or fused ring systems are joined directly to one another or together. 
     
     
       10. The process according to  claim 1 , wherein said amine is any amine that deprotonates a surface hydroxyl. 
     
     
       11. The process according to  claim 1 , wherein said supported silyl-capped silica-bound anion activator is a trialkylsilyl-capped silica-bound anion. 
     
     
       12. The process according to  claim 1 , wherein said metal oxide support is silica. 
     
     
       13. The process according to  claim 1 , wherein said catalyst precursor is chosen from any olefin polymerization catalyst precursor. 
     
     
       14. The process according to  claim 1 , wherein said support is chosen from: silica, fumed silica, alumina, silica-alumina, magnesia, titania, zirconia, silica-chromium, silica-titania, and mixtures thereof. 
     
     
       15. A polymerization process comprising contacting one or more monomers polymerizable by coordination polymerization under suitable polymerization conditions with a polymerization catalyst formed by the method comprising:
 reacting a metal oxide support with at least one silane compound having the general formula: H x Si(R) 4-x , wherein x is 1; and R is a hydrido, alkyl, aryl, heteroalkyl, or heteroaryl ligand, in the presence of a first Lewis acid, thereby generating a silyl capped support; 
 reacting said silyl capped support with a second Lewis acid, which may be the same or different as said first Lewis acid, and an amine, thereby forming a supported silyl-capped silica-bound anion activator; and 
 reacting said supported silyl-capped silica-bound anion activator with at least one catalyst precursor, thereby forming said polymerization catalyst, wherein said first and/or second Lewis acid is an acid having the general formula:
   R x B(ArHal) 3-x , 
 
 where x can equal 0, 1, 2, or 3; R is a monoanionic ligand; B is boron; and ArHal is a halogenated C 6  aromatic or higher carbon number polycyclic aromatic hydrocarbon or aromatic ring assembly in which two or more rings or fused ring systems are joined directly to one another or together. 
 
     
     
       16. The process according to  claim 1 , wherein said amine is any amine that deprotonates a surface hydroxyl. 
     
     
       17. The process according to  claim 1 , wherein said supported silyl-capped silica-bound anion activator is trialkylsilyl-capped silica-bound anion. 
     
     
       18. The process according to  claim 1 , wherein all reactions are conducted in a single reaction vessel. 
     
     
       19. The process of  claim 1 , wherein the silane is selected from the group consisting of: methylsilane, dimethylsilane, trimethylsilane, ethylsilane, diethylsilane, propylsilane, di(n-propyl)silane, tri(n-propyl)silane, phenylsilane, diphenylsilane, triphenylsilane, diethylphenylsilane, ethyldiphenylsilane, diethylperfluorophenylsilane, and trisperfluorophenylsilane. 
     
     
       20. The process of  claim 1 , wherein the monomer is propylene. 
     
     
       21. The process of  claim 1 , wherein the polymerization catalyst is selected from the group consisting of rac-dimethylsilyl-bis(indenyl)hafniumdimethyl, rac-dimethylsilyl-bis(indenyl)zirconiumdimethyl, rac-dimethylsilyl-bis(2-methyl-4-phenyl-indenyl)hafniumdimethyl, rac-dimethylsilyl-bis(2-methyl-4-phenyl-indenyl)zirconiumdimethyl, rac-dimethylsilyl-bis(2-methyl-benzindenyl)hafniumdimethyl, rac-dimethylsilyl-bis(2-methyl-benzindenyl)zirconiumdimethyl, rac-dimethylsilyl-bis-(2-methyl-indenyl)zirconiumdimethyl, rac-dimethylsilyl-bis-(2-methyl-indenyl)hafniumdimethyl, rac-dimethylsilyl-bis(2-methyl-4-naphthyl-indenyl)hafniumdimethyl, rac-dimethylsilyl-bis(2-methyl-4-naphthyl-indenyl)zirconiumdimethyl, rac-ethylene-bis(indenyl)hafniumdimethyl, rac-ethylene-bis(indenyl)zirconiumdimethyl, rac-dimethylsilyl-bis(2-methyl-4-(2′-methyl-phenyl)-indenyl)hafniumdimethyl, rac-dimethylsilyl-bis(2-methyl-4-(2′-methyl-phenyl)-indenyl)zirconiumdimethyl, rac-dimethylsilyl-bis(2-methyl-4-(4′-methyl-phenyl)-indenyl)hafniumdimethyl, rac-dimethylsilyl-bis(2-methyl-4-(4′-methyl-phenyl)-indenyl)zirconiumdimethyl, rac-dimethylsilyl-bis(2-methyl-4-(4′-tert-butyl-phenyl)-indenyl)hafniumdimethyl, rac-dimethylsilyl-bis(2-methyl-4-(4′-tert-butyl-phenyl)-indenyl)zirconiumdimethyl, rac-dimethylsilyl-bis(2-methyl-4-(4′-tert-butyl-phenyl)-indenyl)hafniumdimethyl, rac-dimethylsilyl-bis(2-methyl-4-(4′-tert-butyl-phenyl)-indenyl)zirconiumdimethyl, rac-dimethylsilyl-(2-methyl-4-(4′-tert-butyl-phenyl)-indenyl)(2-isopropyl-4-(4′-tert-butyl-phenyl)-indenyl)hafniumdimethyl, rac-dimethylsilyl-(2-methyl-4-(4′-tert-butyl-phenyl)-indenyl)(2-isopropyl-4-(4′-tert-butyl-phenyl)-indenyl)zirconiumdimethyl, rac-dimethylsilyl-bis(2-methyl-4,6-diisopropyl-indenyl)hafniumdimethyl, rac-dimethylsilyl-bis(2-methyl-4,6-diisopropyl-indenyl)zirconiumdimethyl, Bis(cyclopentadienyl)zirconiumdimethyl, Bis(pentamethylcyclopentadienyl)zirconiumdimethyl, Bis(cyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdimethyl, Bis(1-methyl,4-butylcyclopentadienyl)zirconiumdimethyl, Bis(1-methyl,4-butylcyclopentadienyl)zirconiumdibenzyl, Bis(1-methyl,4-butylcyclopentadienyl)zirconiumdiamide, Bis(1-methyl,4-ethylcyclopentadienyl)zirconiumdimethyl, Bis(1-methyl,4-benzylcyclopentadienyl)zirconiumdimethyl, Bis(1-methyl,3-butylcyclopentadienyl)zirconiumdimethyl, Bis(1-methyl,3-n-propylcyclopentadienyl)zirconiumdimethyl, Bis(1-methyl,3-iso-propylcyclopentadienyl)zirconiumdimethyl, Bis(1,3-dimethylcyclopentadienyl)zirconiumdimethyl, Bis(n-propylcyclopentadienyl)zirconiumdimethyl, Bis(n-propylcyclopentadienyl)zirconiumdiamide, Bis(n-propylcyclopentadienyl)zirconiumdibenzyl, Bis(n-propylcyclopentadienyl)hafniumdimethyl, Bis(n-propylcyclopentadienyl)hafniumdiamide, Bis(n-propylcyclopentadienyl)hafniumdibenzyl, Bis(n-propylcyclopentadienyl)hafniumdimethoxide, Bis(n-butylcyclopentadienyl)zirconiumdimethyl, Bis(tert-butylcyclopentadienyl)zirconiumdimethyl, Bis(benzylcyclopentadienyl)zirconiumdimethyl, Bis(benzylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdimethyl, Bis(propylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdimethyl, Bis(propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdimethyl, Bis(tetramethyl,propylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconium-dimethyl, Bis(tetramethyl,propylcyclopentadienyl)(cyclopentadienyl)zirconiumdimethyl, Dimethylsilylbis(cyclopentadienyl)zirconiumdimethyl, Dimethylsilylbis(cyclopentadienyl)zirconiumdiamide, Dimethylsilylbis(pentamethylcyclopentadienyl)zirconiumdimethyl, Dimethylsilylbis(pentamethylcyclopentadienyl)zirconiumdiamide, Dimethylsilylbis(pentamethylcyclopentadienyl)zirconiumdibenzyl, Dimethylsilylbis(cyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdimethyl, Dimethylsilylbis(cyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdiamide, Dimethylsilylbis(cyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdibenzyl, Dimethylsilylbis(1-methyl,4-butylcyclopentadienyl)zirconiumdimethyl, Dimethylsilylbis(1-methyl,4-butylcyclopentadienyl)zirconiumdiamide, Dimethylsilylbis(1-methyl,4-butylcyclopentadienyl)zirconiumdimethoxide, Dimethylsilylbis(1-methyl,4-butylcyclopentadienyl)zirconiumdibenzyl, Dimethylsilylbis(1-methyl,4-ethylcyclopentadienyl)zirconiumdimethyl, Dimethylsilylbis(1-methyl,4-benzylcyclopentadienyl)zirconiumdimethyl, Dimethylsilylbis(1-methyl,3-butylcyclopentadienyl)zirconiumdimethyl, Dimethylsilylbis(1-methyl,3-n-propylcyclopentadienyl)zirconiumdimethyl, Dimethylsilylbis(1-methyl,3-iso-propylcyclopentadienyl)zirconiumdimethyl, Dimethylsilylbis(1,3-dimethylcyclopentadienyl)zirconiumdimethyl, Dimethylsilylbis(n-propylcyclopentadienyl)zirconiumdimethyl, Dimethylsilylbis(n-butylcyclopentadienyl)zirconiumdimethyl, Dimethylsilylbis(tert-butylcyclopentadienyl)zirconiumdimethyl, Dimethylsilylbis(benzylcyclopentadienyl)zirconiumdimethyl, Dimethylsilylbis(benzylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconium-dimethyl, Dimethylsilylbis(propylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconium-dimethyl, Dimethylsilylbis(propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconium-dimethyl, Dimethylsilylbis(tetramethyl,propylcyclopentadienyl)(pentamethylcyclopentadienyl)-zirconiumdimethyl, and Dimethylsilylbis(tetramethyl,propylcyclopentadienyl)(cyclopentadienyl)zirconium-dimethyl. 
     
     
       22. The process of  claim 1 , wherein the polymerization catalyst is selected from the group consisting of: rac-dimethylsilyl-bis(2-methyl-4-phenyl-indenyl)hafniumdimethyl, and rac-dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdimethyl.